Selective Carbanion-Pyridine Coordination of a Reactive P,N Ligand to Rh-^I

Ligands with reactive carbon sites in the periphery of a metal center have emerged as a powerful approach for metal–ligand bond activation. These reactive carbon sites are commonly generated by deprotonation strategies. Carbon–silicon bond cleavage is a potential alternative to access such constructs. Herein, the monodesilylation of bis‐silyl‐substituted P,N scaffold PN^Si2 in the coordination sphere of [Rh^I(Cl)(CO)(PN^Si2)] (1) with sodium azide is disclosed. This affords a unique dinucleating anionic κ²‐C,N‐κ¹‐P ligand with a carbanionic methine carbon atom directly bound to rhodium as part of a four‐membered Rh‐N‐C‐C rhodacycle. This dimer undergoes meta‐pyridine C−H activation facilitated by weak bases, which leads to a desymmetrization of the system and provides a σ,π‐bridging 3‐pyridyl fragment bound to Rh^I. The facile Si−C cleavage strategy may pave the way to studying the reactivity and functionalization of a variety of κ²‐C,N‐coordinated pyridine scaffolds for selective transformations.